WO2017082231A1 - Composition de résine de polyamide et article moulé obtenu par moulage de cette dernière - Google Patents

Composition de résine de polyamide et article moulé obtenu par moulage de cette dernière Download PDF

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WO2017082231A1
WO2017082231A1 PCT/JP2016/083044 JP2016083044W WO2017082231A1 WO 2017082231 A1 WO2017082231 A1 WO 2017082231A1 JP 2016083044 W JP2016083044 W JP 2016083044W WO 2017082231 A1 WO2017082231 A1 WO 2017082231A1
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polyamide
resin composition
metal salt
mass
polyamide resin
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PCT/JP2016/083044
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English (en)
Japanese (ja)
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淳一 三井
竹谷　豊
泰生 上川
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ユニチカ株式会社
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Priority to JP2017510417A priority Critical patent/JP6129464B1/ja
Priority to CN201680065843.7A priority patent/CN108350271B/zh
Publication of WO2017082231A1 publication Critical patent/WO2017082231A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyamide resin composition having flame retardancy.
  • Polyamide has excellent heat resistance and mechanical properties, and is used as many electrical / electronic parts and parts around automobile engines. Among these parts, polyamides used for electric and electronic parts are required to have higher flame retardancy.
  • Patent Document 1 discloses the use of a mixture of a reaction product of melamine and phosphoric acid, a phosphinic acid metal salt, and a metal compound as a non-halogen flame retardant, both of which are 1/16 inch. It is disclosed that molded products satisfy the flame retardant standard UL94V-0 standard.
  • polyamide resin compositions containing phosphinic acid metal salts are highly corrosive to metals, and during melt processing, the metal parts such as extruder screws and dies, and molding machine screws and molds are severely worn. There was a problem of lack of mass productivity. In addition, this composition has a problem that a lot of gas is generated during the molding process, and dirt adheres to the mold.
  • Patent Document 2 As a method for suppressing metal corrosiveness and gas generation with respect to these problems, a technique of blending an auxiliary agent is disclosed.
  • Patent Document 3 calcium oxide is used, and in Patent Document 3, a salicylic acid derivative is used as an auxiliary agent.
  • Patent Document 4 discloses a technique of compounding an inorganic aluminum compound with polyamide having a specific structure, and Patent Document 5 discloses a technique of extruding under specific conditions.
  • the present invention solves the above-mentioned problems in a polyamide resin composition containing a metal salt of phosphinic acid and has excellent flame retardancy while suppressing metal corrosiveness during melt processing, and molding processing
  • An object of the present invention is to provide a polyamide resin composition capable of reducing the generation of gas and the adhesion of dirt to a mold.
  • the inventors of the present invention improve flame retardancy by incorporating a specific amount of a specific compound in a polyamide resin composition containing a phosphinic acid metal salt. I found. Thereby, content of a phosphinic acid metal salt can be reduced, the problem resulting from a phosphinic acid metal salt can be solved, and it reached
  • a polyamide resin composition comprising a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine compound (C) having a hindered phenol structure
  • the mass ratio (A / B) of the polyamide (A) and the phosphinic acid metal salt (B) is 60/40 to 95/5
  • the content of the hydrazine-based compound (C) having a hindered phenol structure is 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B).
  • a polyamide resin composition (2) The polyamide resin composition as described in (1), wherein the polyamide (A) has a melting point of 270 to 350 ° C.
  • the polyamide (A) contains a semi-aromatic polyamide and an aliphatic polyamide, and has a mass ratio (semi-aromatic polyamide / aliphatic polyamide) of 70/30 to 40/60 ( 1) The polyamide resin composition as described.
  • R 1 , R 2 , R 4 and R 5 each independently represents a linear or branched alkyl group having 1 to 16 carbon atoms or a phenyl group.
  • R 3 represents a linear or branched group.
  • the chain represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group, and M represents a calcium ion, an aluminum ion, a magnesium ion, or a zinc ion. Is 2 or 3.
  • a reinforcing material (D) is further contained, and the content thereof is 5 to 200 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B).
  • the polyamide resin composition according to any one of (1) to (5).
  • at least one metal selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, borate metal salts, metal stannates, fatty acid metal salts, hydrotalcite and derivatives thereof.
  • Compound (E) is contained, and the content thereof is 0.01 to 8 parts by mass with respect to 100 parts by mass in total of polyamide (A) and phosphinic acid metal salt (B) (1 ) To (6).
  • the metal compound (E) contains a carbonate metal salt and a fatty acid metal salt, and the mass ratio (metal carbonate salt / fatty acid metal salt) is 90/10 to 30/70 (7 ) Polyamide resin composition.
  • (9) A molded article obtained by molding the polyamide resin composition according to any one of (1) to (8) above.
  • the present invention it is possible to provide a flame-retardant polyamide resin composition in which the content of the metal phosphinate is reduced and the problems of metal corrosivity and gas generation caused by the content are solved. Since the content of the acid metal salt is reduced, a molded article having excellent mechanical properties can be provided.
  • the polyamide resin composition of the present invention contains a polyamide (A), a phosphinic acid metal salt (B), and a hydrazine compound (C) having a hindered phenol structure.
  • the polyamide (A) includes, from the classification of polymerization methods, polycondensates of dicarboxylic acids and diamines, ring-opening polymers of cyclic lactams, polycondensates of aminocarboxylic acids, and the like. From the classification, mention may be made of aliphatic polyamides, semi-aromatic polyamides, alicyclic polyamides, and copolymers thereof. As the polyamide (A), these polyamides may be used alone, or a copolymer or a mixture of two or more kinds of polyamides may be used.
  • aliphatic polyamide examples include polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 612, polyamide 1010, and the like.
  • semi-aromatic polyamides include polyamide 4T (T: terephthalic acid), polyamide 4I (I: isophthalic acid), polyamide 6I, polyamide 7T, polyamide 8T, polyamide 9T, polyamide 10T, polyamide 11T, polyamide 12T, polyamide MXD6. (MXD: metaxylylenediamine) and the like.
  • alicyclic polyamide examples include polyamide 6C (C: 1,4-cyclohexanedicarboxylic acid), polyamide 7C, polyamide 8C, polyamide 9C, polyamide 10C, polyamide 11C, and polyamide 12C.
  • the copolymer for example, when the diamine has 6 carbon atoms, PA66 / 6, PA6T / 6, PA6T / 12, PA6T / 46, PA6T / 66, PA6T / 610, PA6T / 612, PA6T / 6I, PA6T / 6I / 66, PA6T / M5T (M5: methylpentadiamine), PA6T / TM6T (TM6: 2,2,4- or 2,4,4-trimethylhexamethylenediamine), PA6T / MMCT (MMC: 4, 4'-methylenebis (2-methylcyclohexylamine)) and the like.
  • M5T methylpentadiamine
  • PA6T / TM6T TM6: 2,2,4- or 2,4,4-trimethylhexamethylenediamine
  • PA6T / MMCT MMC: 4, 4'-methylenebis (2-methylcyclohexylamine)
  • the polyamide (A) preferably has a melting point of 270 ° C. to 350 ° C. Since the polyamide (A) has a melting point of 270 ° C. or higher, it has heat resistance and can withstand a reflow process in which the maximum temperature is about 260 ° C. On the other hand, when the melting point of the polyamide (A) exceeds 350 ° C., the decomposition temperature of the amide bond is about 350 ° C., so that carbonization and decomposition may proceed during melt processing. As the polyamide (A) having heat resistance, polyamide 46, polyamide 6T, polyamide 9T, polyamide 10T, and copolymers thereof are preferable because of their high industrial versatility.
  • polyamide 6T, polyamide 9T, polyamide 10T, and copolymers thereof are more preferable because they are particularly excellent in reflow resistance from the viewpoint of high heat resistance and low water absorption, and polyamide 10T and copolymers thereof are particularly preferable. preferable.
  • the semi-aromatic polyamide preferably comprises a monocarboxylic acid component as a constituent component.
  • the content of the monocarboxylic acid component is preferably 0.3 to 4.0 mol%, and preferably 0.3 to 3.0 mol%, based on all monomer components constituting the semiaromatic polyamide. More preferably, it is 0.3 to 2.5 mol%, more preferably 0.8 to 2.5 mol%.
  • the semi-aromatic polyamide contains a monocarboxylic acid component within the above range, so that the molecular weight distribution at the time of polymerization can be reduced, the releasability at the time of molding processing can be improved, or the gas at the time of molding processing can be improved. The generation amount can be suppressed.
  • the content of monocarboxylic acid component refers to the proportion of the monocarboxylic acid residue in the semi-aromatic polyamide, that is, the proportion of the monocarboxylic acid from which the terminal hydroxyl group is eliminated.
  • the semi-aromatic polyamide preferably contains a monocarboxylic acid having a molecular weight of 140 or more, more preferably a monocarboxylic acid having a molecular weight of 170 or more as a monocarboxylic acid component.
  • the molecular weight of the monocarboxylic acid is 140 or more, the releasability is improved, the amount of gas generated can be suppressed at the temperature during the molding process, and the molding fluidity can also be improved.
  • Examples of the monocarboxylic acid component include aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, and aromatic monocarboxylic acid. Among them, the amount of generated gas of the polyamide-derived component is reduced, mold contamination is reduced, and release is performed. An aliphatic monocarboxylic acid is preferable because it can improve moldability.
  • Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Of these, stearic acid is preferred because of its high versatility.
  • Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
  • aromatic monocarboxylic acid having a molecular weight of 140 or more examples include 4-ethylbenzoic acid, 4-hexylbenzoic acid, 4-laurylbenzoic acid, 1-naphthoic acid, 2-naphthoic acid and derivatives thereof. .
  • the monocarboxylic acid component may be used alone or in combination.
  • a monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may be used in combination.
  • the molecular weight of the monocarboxylic acid refers to the molecular weight of the starting monocarboxylic acid.
  • the polyamide (A) preferably contains a semi-aromatic polyamide, and the semi-aromatic polyamide, as described above, has an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid having a molecular weight of 140 or more. It is preferably composed of an acid component, and the content of the monocarboxylic acid component is preferably 0.3 to 4.0 mol% with respect to the total monomer components constituting the semi-aromatic polyamide.
  • the polyamide (A) preferably contains a semi-aromatic polyamide and an aliphatic polyamide, and the mass ratio of the semi-aromatic polyamide and the aliphatic polyamide (semi-aromatic polyamide / aliphatic polyamide) is 70/30 to 40/60.
  • the polyamide (A) contains an aliphatic polyamide in the above ratio together with a semi-aromatic polyamide, the polyamide (A) has heat resistance derived from the semi-aromatic polyamide and also has high fluidity derived from the aliphatic polyamide. It becomes possible to design an excellent resin composition.
  • the aliphatic polyamide contained together with the semi-aromatic polyamide preferably has a melting point of 200 to 300 ° C.
  • polyamide 6, polyamide 66 and polyamide 46 are preferred. 6.
  • Polyamide 66 is more preferable
  • the polyamide (A) preferably has a melt flow rate (MFR) of 1 to 200 g / 10 min when measured with a load of 1.2 kgf (melting point + 15 ° C.) according to JIS K7210. More preferably, it is ⁇ 150 g / 10 min, and further preferably 20-100 g / 10 min. MFR can be used as an index of molding fluidity, and the higher the MFR value, the higher the fluidity. When the MFR of the polyamide (A) exceeds 200 g / 10 minutes, the mechanical properties of the resulting resin composition may be deteriorated. When the MFR of the polyamide (A) is less than 1 g / 10 minutes, the fluidity may be reduced. It is extremely low and may not be melt processed. When the polyamide (A) contains a plurality of polyamides having different melting points, the MFR of the polyamide (A) is measured at the melting point of the polyamide having the highest melting point + 15 ° C.
  • the polyamide (A) can be produced using a conventionally known method such as a heat polymerization method or a solution polymerization method. Of these, the heat polymerization method is preferably used because it is industrially advantageous.
  • the polyamide resin composition of the present invention contains a phosphinic acid metal salt (B).
  • the mass ratio of polyamide (A) and phosphinic acid metal salt (B) (polyamide (A) / phosphinic acid metal salt (B)) needs to be 60/40 to 95/5. 70/30 to 92/8.
  • the ratio of the phosphinic acid metal salt (B) is less than 5% by mass, it is difficult to impart the required flame retardancy to the resin composition.
  • the ratio of the phosphinic acid metal salt (B) exceeds 40% by mass, the resin composition is excellent in flame retardancy, but the metal corrosivity becomes large and melt kneading may be difficult.
  • the molded product obtained may have insufficient mechanical properties.
  • Examples of the phosphinic acid metal salt (B) of the present invention include phosphinic acid metal salts represented by the following general formula (I) and diphosphinic acid metal salts represented by the general formula (II).
  • each of R 1 , R 2 , R 4 and R 5 independently needs to be a linear or branched alkyl group having 1 to 16 carbon atoms or a phenyl group, and has 1 to 8 carbon atoms.
  • R 1 and R 2 and R 4 and R 5 may form a ring with each other.
  • R 3 must be a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an arylalkylene group, or an alkylarylene group.
  • Examples of the linear or branched alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, isopropylidene group, n-butylene group, tert-butylene group, n- A pentylene group, an n-octylene group, and an n-dodecylene group may be mentioned.
  • Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group.
  • Examples of the alkylarylene group include a methylphenylene group, an ethylphenylene group, a tert-butylphenylene group, a methylnaphthylene group, an ethylnaphthylene group, and a tert-butylnaphthylene group.
  • Examples of the arylalkylene group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group.
  • M represents a metal ion.
  • Examples of the metal ions include calcium ions, aluminum ions, magnesium ions, and zinc ions. Aluminum ions and zinc ions are preferable, and aluminum ions are more preferable.
  • m and n represent the valence of the metal ion. m is 2 or 3.
  • a represents the number of metal ions
  • b represents the number of diphosphinic acid ions
  • the phosphinic acid metal salt and diphosphinic acid metal salt are produced in an aqueous solution using the corresponding phosphinic acid and diphosphinic acid and metal carbonate, metal hydroxide or metal oxide, respectively, and usually exist as monomers. Depending on the reaction conditions, it may exist in the form of a polymeric phosphinic acid salt with a degree of condensation of 1 to 3.
  • phosphinic acid salt represented by the general formula (I) include, for example, calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, ethylmethylphosphine.
  • aluminum diethylphosphinate and zinc diethylphosphinate are preferable, and
  • diphosphinic acid used in the production of diphosphinic acid salts include methanodi (methylphosphinic acid) and benzene-1,4-di (methylphosphinic acid).
  • diphosphinic acid salt represented by the general formula (II) include, for example, calcium methanedi (methylphosphinate), methanedi (methylphosphinic acid) magnesium, methanedi (methylphosphinic acid) aluminum, and methanedi (methylphosphinic acid).
  • Zinc Zinc, benzene-1,4-di (methylphosphinic acid) calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-di (methylphosphinic acid) aluminum, benzene-1,4 -Di (methylphosphinic acid) zinc.
  • methanedi (methylphosphinic acid) aluminum and methanedi (methylphosphinic acid) zinc are preferable because of excellent balance between flame retardancy and electrical characteristics.
  • Specific products of the phosphinic acid metal salt (B) include, for example, “Exolit OP1230”, “Exolit OP1240”, “Exolit OP1312”, “Exolit OP1314”, and “Exolit OP1400” manufactured by Clariant.
  • the hydrazine compound (C) having a hindered phenol structure used in the present invention has both a hindered phenol structure having an effect of capturing peroxy radicals and a hydrazine structure chelating metal ions.
  • Specific examples include compounds represented by the following formula (III).
  • the flame retardancy of the polyamide can be dramatically improved. Therefore, the compounding quantity of a phosphinic acid metal salt (B) can be reduced, and the metal corrosivity which is a subject of the polyamide resin composition containing a phosphinic acid metal salt can be suppressed.
  • Specific products of the hydrazine-based compound (C) having a hindered phenol structure include, for example, “CDA-10” manufactured by Adeka, “IRGANOX MD 1024” manufactured by BASF.
  • the content of the hydrazine compound (C) having a hindered phenol structure should be 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). It is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass. If the content of the hydrazine-based compound (C) having a hindered phenol structure is less than 0.01 parts by mass, the effect of improving the flame retardancy cannot be obtained, while if the content exceeds 5 parts by mass, it is difficult. Not only does the fuel efficiency become saturated and no further improvement effect can be expected, but the resulting molded article may have insufficient mechanical strength.
  • the polyamide resin composition of the present invention has dramatically improved flame retardancy.
  • the flame retardancy efficiency is high, the blending amount of the phosphinic acid metal salt (B) can be reduced while ensuring sufficient flame retardancy. Therefore, the metal corrosivity which was the subject of the polyamide resin composition containing a phosphinic acid metal salt (B) can be improved significantly. That is, it is possible to reduce corrosion and wear of the screw and die of the extruder during the melt extrusion process and the metal parts such as the screw and die of the molding machine during the melt molding process.
  • the above-mentioned metal corrosivity in the polyamide resin composition containing the phosphinic acid metal salt (B) is particularly noticeable in melt processing at high temperatures, and is particularly a problem in heat-resistant polyamides having a high melting point. In the composition, a particularly excellent effect can be exhibited.
  • the polyamide resin composition of the present invention preferably further contains a reinforcing material (D).
  • a reinforcing material D
  • plate-like reinforcing materials such as talc, glass flake, mica, graphite, metal foil, carbon black, silicon carbide, silica, quartz powder, fused silica, glasses (glass beads, glass powder, milled) Spherical reinforcing materials such as glass fibers), silicates (calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, etc.), sulfates (calcium sulfate, barium sulfate, etc.), and fibrous reinforcing materials shown below Is mentioned.
  • the fibrous reinforcing material is not particularly limited.
  • glass fiber, carbon fiber, boron fiber, asbestos fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polybenzoxazole fiber, polytetrafluoro Examples include ethylene fiber, kenaf fiber, bamboo fiber, hemp fiber, bagasse fiber, high-strength polyethylene fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, and basalt fiber.
  • glass fiber, carbon fiber, and metal fiber are preferable because they have a high effect of improving mechanical properties, have heat resistance that can withstand the heating temperature during melt kneading with polyamide (A), and are easily available.
  • the fibrous reinforcing material may be used alone or in combination.
  • the glass fiber and carbon fiber are preferably surface-treated with a silane coupling agent.
  • the silane coupling agent may be dispersed in the sizing agent.
  • examples of the silane coupling agent include vinyl silanes, acrylic silanes, epoxy silanes, and amino silanes.
  • amino silane cups have a high adhesion effect between polyamide (A) and glass fibers or carbon fibers.
  • a ring agent is preferred.
  • the fiber length and fiber diameter of the fibrous reinforcing material are not particularly limited, but the fiber length is preferably 0.1 to 7 mm, and more preferably 0.5 to 6 mm.
  • the resin composition can be reinforced without adversely affecting the moldability.
  • the fiber diameter is preferably 3 to 20 ⁇ m, more preferably 5 to 13 ⁇ m.
  • the resin composition can be reinforced without breaking during melt-kneading.
  • Examples of the cross-sectional shape of the fibrous reinforcing material include a circular shape, a rectangular shape, an elliptical shape, and other irregular cross-sections. A circular shape is preferable among them.
  • the content of the reinforcing material (D) is preferably 5 to 200 parts by mass with respect to a total of 100 parts by mass of the polyamide (A) and the phosphinic acid metal salt (B).
  • the amount is more preferably 10 to 180 parts by mass, further preferably 20 to 150 parts by mass, and particularly preferably 30 to 130 parts by mass.
  • the content of the reinforcing material (D) is less than 5 parts by mass, the effect of improving mechanical properties may be small.
  • the polyamide resin composition of the present invention preferably further contains a metal compound (E).
  • a metal compound (E) As described above, the polyamide resin composition of the present invention contains the hydrazine compound (C) having a hindered phenol structure, thereby reducing the content of the phosphinic acid metal salt (B), and at the time of melt processing.
  • metal corrosivity can be suppressed, metal corrosivity can be further suppressed by containing a metal compound (E).
  • the content of the metal compound (E) is preferably 0.01 to 8 parts by mass, and 0.05 to 3 parts by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). Part is preferable, and 0.1 to 2 parts by mass is more preferable. If the content of the metal compound (E) is less than 0.01 parts by mass, the effect of suppressing metal corrosivity cannot be obtained. On the other hand, when the content of the metal compound (E) exceeds 8 parts by mass, the effect of suppressing metal corrosivity is saturated, and not only a further suppression effect cannot be expected, but the mechanical strength of the obtained molded body is high. It may be insufficient.
  • the metal compound (E) is selected from the group consisting of metal oxide, metal hydroxide, carbonate metal salt, borate metal salt, metal stannate, fatty acid metal salt, hydrotalcite and derivatives thereof. Or a mixture of two or more.
  • the metal contained in a metal compound (E) is not specifically limited, For example, calcium, zinc, iron, aluminum, magnesium, silicon etc. are mentioned.
  • the metal oxide include zinc oxide, iron oxide, calcium oxide, aluminum oxide (alumina), magnesium oxide, and silicon oxide (silica).
  • the metal hydroxide include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and alumina hydrate (boehmite).
  • the metal carbonate include calcium carbonate and magnesium carbonate.
  • boric acid metal salt examples include zinc borate, magnesium borate, calcium borate, aluminum borate and the like.
  • metal stannate examples include zinc stannate.
  • fatty acid metal salt examples include lithium salt, calcium salt, barium salt, zinc salt or aluminum salt of montanic acid, behenic acid or stearic acid.
  • the metal compound (E) may be one kind of the above-mentioned compounds, or may be a mixture of two or more kinds.
  • the metal compound (E) contains a carbonate metal salt and a fatty acid metal salt, and has a mass ratio (metal carbonate / When the (fatty acid metal salt) is 90/10 to 30/70, the resin composition can suppress the metal corrosivity without decreasing the flame retardancy.
  • the polyamide resin composition of the present invention may further contain a flame retardant aid.
  • a flame retardant aid include nitrogen-based flame retardants, nitrogen-phosphorous flame retardants, and inorganic flame retardants.
  • nitrogen-based flame retardants include melamine compounds, cyanuric acid or isocyanuric acid and melamine compound salts.
  • the melamine compounds include melamine, melamine derivatives, compounds having a structure similar to melamine, condensates of melamine, and the like, specifically, melamine, ammelide, ammelin, formoguanamine, guanylmelamine, cyano.
  • examples thereof include compounds having a triazine skeleton such as melamine, benzoguanamine, acetoguanamine, succinoguanamine, melam, melem, methone and melon, and sulfates and melamine resins thereof.
  • the salt of cyanuric acid or isocyanuric acid and a melamine compound is an equimolar reaction product of cyanuric acid or isocyanuric acid and a melamine compound.
  • nitrogen-phosphorous flame retardants include adducts (melamine adducts) and phosphazene compounds formed from melamine or its condensation products and phosphorus compounds.
  • adducts melamine adducts
  • phosphazene compounds formed from melamine or its condensation products and phosphorus compounds examples include phosphoric acid, orthophosphoric acid, phosphonic acid, phosphinic acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, and polyphosphoric acid.
  • Specific examples of the melamine adduct include melamine phosphate, melamine pyrophosphate, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate, and melam polyphosphate, among which melamine polyphosphate is preferable.
  • the number of phosphorus is preferably 2 or more, and more preferably 10 or more.
  • Specific examples of phosphazene compounds include “Ravitor FP-100” and “Ravitor FP-110” manufactured by Fushimi Pharmaceutical Co., Ltd., “SPS-100” and “SPB-100” manufactured by Otsuka Chemical Co., Ltd. .
  • inorganic flame retardant examples include metal hydroxides such as magnesium hydroxide and calcium hydroxide, zinc salts such as zinc borate and zinc phosphate, and calcium aluminate. Although many of these inorganic flame retardants overlap with the above metal compound (E), they may be blended for either purpose of improving flame retardancy or reducing metal corrosivity.
  • the polyamide resin composition of the present invention can be further improved in stability and moldability by containing a phosphorus-based antioxidant.
  • the phosphorus antioxidant may be either an inorganic compound or an organic compound.
  • examples of the phosphorus antioxidant include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, Phenyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (" ADEKA STAB PEP-36 "), bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite (" ADEKA STAB PEP-36 "
  • the phosphorus-based antioxidant is easily mixed uniformly with the phosphinic acid metal salt (B) and prevents decomposition, so that flame retardancy can be improved.
  • the phosphorus-based antioxidant can prevent the polyamide (A) from being decomposed and its molecular weight is reduced, and can improve operability, moldability, and mechanical properties during melt processing.
  • the content of the phosphorus-based antioxidant is preferably 0.1 to 3 parts by mass, preferably 0.1 to 1 part by mass with respect to 100 parts by mass in total of the polyamide (A) and the phosphinic acid metal salt (B). More preferably.
  • the polyamide resin composition of the present invention may further contain other stabilizers, colorants, antistatic agents, carbonization inhibitors and other additives as necessary.
  • the colorant include pigments such as titanium oxide, zinc oxide, and carbon black, and dyes such as nigrosine.
  • the stabilizer include hindered phenol-based antioxidants, sulfur-based antioxidants, light stabilizers, heat stabilizers composed of copper compounds, and heat stabilizers composed of alcohols.
  • the carbonization inhibitor is an additive that improves tracking resistance, and examples thereof include inorganic substances such as metal hydroxides and metal borate salts, and the above heat stabilizers.
  • the method for producing the resin composition of the present invention is not particularly limited, but is added as necessary, such as polyamide (A), phosphinic acid metal salt (B), hydrazine-based compound (C) having a hindered phenol structure, and the like.
  • a method in which a reinforcing material (D), a metal compound (E), other additives and the like are blended and melt-kneaded is preferable.
  • the melt-kneading method include a method using a batch kneader such as Brabender, a Banbury mixer, a Henschel mixer, a helical rotor, a roll, a single screw extruder, a twin screw extruder and the like.
  • the melt kneading temperature is selected from a region where the polyamide (A) melts and the polyamide (A) does not decompose. If the melt kneading temperature is too high, not only the polyamide (A) is decomposed but also the metal phosphinate (B) may be decomposed. Therefore, when the melting point of the polyamide (A) is Tm, (Tm ⁇ 20 ° C.) to (Tm + 50 ° C.).
  • a method of extruding the molten mixture into a strand shape to form a pellet As a method of processing the polyamide resin composition of the present invention into various shapes, a method of extruding the molten mixture into a strand shape to form a pellet, a method of hot-cutting the molten mixture, underwater cutting to form a pellet, Examples include a method of extrusion cutting into a sheet shape, and a method of extrusion pulverization into a block shape to form a powder.
  • Examples of the molding method of the polyamide resin composition of the present invention include an injection molding method, an extrusion molding method, a blow molding method, and a sintering molding method.
  • a molding method is preferred.
  • the injection molding machine is not particularly limited, and examples thereof include a screw inline type injection molding machine and a plunger type injection molding machine.
  • the polyamide resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled to a predetermined shape and solidified, and then as a molded body from the mold. It is taken out.
  • the resin temperature during injection molding is preferably heated and melted at a melting point (Tm) or higher of the polyamide (A), and more preferably less than (Tm + 50 ° C.).
  • Tm melting point
  • A polyamide
  • Tm + 50 ° C. melting point
  • the polyamide resin composition it is preferable to use sufficiently dried polyamide resin composition pellets. If the water content is large, the resin foams in the cylinder of the injection molding machine, and it may be difficult to obtain an optimal molded body.
  • the moisture content of the polyamide resin composition pellets used for injection molding is preferably less than 0.3 parts by mass and more preferably less than 0.1 parts by mass with respect to 100 parts by mass of the polyamide resin composition.
  • the polyamide resin composition of the present invention is excellent in flame retardancy and can be molded while suppressing metal corrosiveness, and is used as a molded article for a wide range of applications such as automobile parts, electrical and electronic parts, sundries, civil engineering and building supplies. it can.
  • automobile parts include a thermostat cover, an IGBT module member of an inverter, an insulator member, an exhaust finisher, a power device housing, an ECU housing, an ECU connector, a motor and a coil insulating material, and a cable covering material.
  • Examples of electrical and electronic components include connectors, LED reflectors, switches, sensors, sockets, capacitors, jacks, fuse holders, relays, coil bobbins, breakers, electromagnetic switches, holders, plugs, portable computers, word processors, and other electrical equipment.
  • Examples include housings for housing parts, resistors, ICs, and LEDs.
  • the polyamide resin composition of the present invention is particularly excellent in flame retardancy, and therefore can be suitably used for electric and electronic parts.
  • the physical properties of the polyamide and the polyamide resin composition were measured by the following methods. In the measurement of the resin composition of Example 30 containing two kinds of polyamides (A-1) and (A-5), the melting point of polyamide (A-1) having a high melting point was applied as the melting point.
  • MFR Melt flow rate
  • the polyamide resin composition was injection molded using an injection molding machine S2000i-100B type (manufactured by FANUC) under conditions of cylinder temperature (melting point + 15 ° C.) and mold temperature (melting point-185 ° C.). Thus, a test piece (dumbbell piece) was produced. Using the obtained test piece, bending strength and bending elastic modulus were measured according to ISO178. Bending strength and bending elastic modulus indicate that the larger the value, the better the mechanical properties.
  • the polyamide resin composition was injection molded using an injection molding machine CND15 (manufactured by Niigata Machine Techno Co., Ltd.) under the conditions of cylinder temperature (melting point + 15 ° C.) and mold temperature (melting point-185 ° C.).
  • a test piece of 5 inches (127 mm) ⁇ 1/2 inch (12.7 mm) ⁇ 1/32 inch (0.79 mm) was produced.
  • flame retardancy was evaluated according to the standards of UL94 (standard defined by Under Writers Laboratories Inc., USA) shown in Table 1. When not satisfying any of the standards, it was set as “not V-2”. A shorter total afterflame time indicates better flame retardancy.
  • the number of molded bodies without pin marks is preferably 90 or more, and more preferably 95 or more.
  • a total of 25 kg of the polyamide resin composition was extruded into the gap under the conditions of the extruder barrel set temperature (melting point + 15 ° C.) and discharge of 7 kg / h.
  • the metal plate (MP) was removed, left in a furnace at 500 ° C. for 10 hours, the adhered resin was removed, the mass was measured, and the metal corrosivity was measured by the mass change before and after extrusion. It shows that metal corrosivity is so small that a mass change is small.
  • Polyamide (A) Polyamide (A-1) 4.70 kg of powdered terephthalic acid (TPA) as a dicarboxylic acid component, 0.32 kg of stearic acid (STA) as a monocarboxylic acid component, and 9.3 g of sodium hypophosphite monohydrate as a polymerization catalyst,
  • TPA powdered terephthalic acid
  • STA stearic acid
  • 9.3 g of sodium hypophosphite monohydrate as a polymerization catalyst
  • the reactor was placed in a ribbon blender reactor and heated to 170 ° C. with stirring at a rotation speed of 30 rpm under nitrogen sealing. Thereafter, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 2.98 kg of 1,10-decanediamine (DDA) (2.98 kg) heated to 100 ° C. as a diamine component was added using a liquid injection device.
  • DDA 1,10-decanediamine
  • the reaction product was obtained by adding continuously (continuous liquid injection method) over 5 hours.
  • the obtained reaction product was polymerized by heating at 250 ° C. and a rotation speed of 30 rpm for 8 hours under a nitrogen stream in the same reaction apparatus to produce a polyamide powder.
  • the obtained polyamide powder was made into a strand using a twin-screw kneader, and the strand was cooled and solidified by passing it through a water tank, and was cut with a pelletizer to obtain polyamide (A-1) pellets.
  • Polyamides (A-2) to (A-4) were obtained in the same manner as polyamide (A-1) except that the resin composition was changed as shown in Table 2.
  • Polyamide (A-5) Polyamide 66 (A125J manufactured by Unitika)
  • Polyamide (A-6) Polyamide 46 (TW300, manufactured by DSM)
  • Table 2 shows the resin compositions and characteristic values of the polyamides (A-1) to (A-6).
  • Phosphinic acid metal salt (B) -B-1 Aluminum diethylphosphinate (Exolit OP1230 manufactured by Clariant)
  • Phosphorus antioxidant F-1 Tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene-di-phosphonite (Hostanox P-EPQ manufactured by Clariant)
  • Triazole compound G-1 2-hydroxy-N-1H-1,2,4-triazol-3-yl-benzamide (CDA-1 manufactured by Adeka)
  • Example 1 75 parts by weight of polyamide (A-1), 25 parts by weight of phosphinic acid metal salt (B-1), 1 part by weight of hydrazine compound (C-1) having a hindered phenol structure, 1 part of metal compound (E-1) Part, 0.3 parts by weight of a phosphorus-based antioxidant (F-1) are dry blended and weighed using a loss-in-weight continuous quantitative supply device CE-W-1 (manufactured by Kubota), screw diameter 26 mm , L / D50, the same direction twin screw extruder TEM26SS type (manufactured by Toshiba Machine Co., Ltd.) was supplied to the main supply port and melt-kneaded.
  • CE-W-1 manufactured by Kubota
  • screw diameter 26 mm screw diameter 26 mm
  • L / D50 the same direction twin screw extruder TEM26SS type
  • the reinforcing material (D-1) was supplied from the side feeder and further kneaded. After taking the strand from the die, it was cooled and solidified by passing through a water tank, and cut with a pelletizer to obtain polyamide resin composition pellets.
  • the barrel temperature of the extruder was set to (melting point ⁇ 5 to + 15 ° C.), screw rotation speed 250 rpm, and discharge rate 25 kg / h.
  • Examples 2 to 32 and Comparative Example A polyamide resin composition pellet was obtained in the same manner as in Example 1 except that the composition of the polyamide resin composition was changed as shown in Tables 3 to 4.
  • the resin composition pellet displayed in Comparative Example nC such as Comparative Example 1C has the same composition as the pellet of the resin composition of Example n except that it does not contain a hydrazine-based compound (C) having a hindered phenol structure. It is.
  • the comparative example does not contain the hydrazine compound (C) having a hindered phenol structure.
  • flame retardancy was improved and metal corrosivity at high temperatures was suppressed.
  • the resin composition was improved in flame retardancy by increasing the content of the hydrazine compound having a hindered phenol structure.
  • the resin composition of Comparative Example 3 was excellent in flame retardancy by containing 45 parts by mass of a phosphinic acid metal salt, but was extremely high in metal corrosivity.
  • the flame retardancy comparable to that obtained in Comparative Example 3 contains a hydrazine-based compound having a hindered phenol structure even when the content of the phosphinic acid metal salt is reduced to 25 to 40 parts by mass. (Examples 11 and 15) obtained in this way, in Examples containing a hydrazine-based compound having a hindered phenol structure, the content of phosphinic acid metal salt can be reduced, and metal corrosivity is suppressed. Became possible.
  • Example 1 From the comparison of Examples 1 to 6, the resin compositions of Examples 1, 2, and 4 containing a monocarboxylic acid having a molecular weight of 140 or more as the monocarboxylic acid component of the polyamide to be used have less mold contamination, The releasability was excellent. From the comparison between Example 1 and Example 3, the resin composition of Example 1 using an aliphatic monocarboxylic acid as the monocarboxylic acid component was more than Example 3 using an aromatic monocarboxylic acid. The releasability was excellent. From the comparison between Example 1 and Example 2, the resin composition of Example 1 using 1,10-decanediamine rather than the resin composition of Example 2 using 1,9-nonanediamine as the aliphatic diamine component. The thing was superior in mechanical properties.
  • the resin composition of Example 6 containing the aliphatic polyamide (A-6) having a high water absorption rate has 1 to 2 blisters on the test piece in the reflow resistance test. Occurrence was seen. However, the resin compositions of all other examples containing a semi-aromatic polyamide containing a terephthalic acid component and having a low water absorption were excellent in reflow resistance, and no change was observed in the appearance of the test piece.
  • the test piece for flame retardancy evaluation was subjected to moisture absorption treatment at 85 ° C. ⁇ 85% RH for 168 hours, and then in an infrared heating type reflow furnace at 150 ° C. for 1 minute. The sample was heated, heated to 265 ° C. at a rate of 100 ° C./min, and held for 10 seconds.
  • the resin composition of Example 1 using glass fiber as a reinforcing material has better mechanical properties than the resin composition of Example 21 using plate-like talc. It was.
  • the resin composition was found to suppress metal corrosivity by containing a metal compound.
  • the resin compositions of Examples 29 and 30 in which the metal compound contains a metal carbonate and a fatty acid metal salt are more incombustible than the resin compositions of Examples 1, 27 and 28 containing one metal compound. It became possible to suppress the decrease in sex.
  • the resin composition of Example 30 has improved fluidity compared to the resin composition of Example 29 in which the polyamide contains only a semi-aromatic polyamide because the polyamide contains a semi-aromatic polyamide and an aliphatic polyamide.
  • the shear heat generation of the resin was suppressed, and the metal corrosiveness could be further suppressed, and the resin had reflow resistance despite containing the aliphatic polyamide.
  • the resin composition was improved in mechanical properties and releasability by containing a phosphorus-based antioxidant.
  • the resin compositions of Examples 7 and 26 have a flame retardancy of V-2
  • the resin composition of Example 8 has a flame retardance of V-1, and is flame retardant as compared with the resin compositions of other examples.
  • the metal corrosivity was greatly suppressed.
  • the resin compositions of Comparative Examples 1 and 2 were inferior in flame retardancy because they did not contain phosphinic acid metal salt or the content thereof was small. Since the resin composition of Comparative Example 3 had a high content of phosphinic acid metal salt, it was excellent in flame retardancy, but the metal corrosivity was remarkably increased. In Comparative Examples 4 to 6, when the resin composition contained a hydrazine compound having a hindered phenol structure, the flame retardancy was further improved, but the metal corrosivity was not suppressed. In Comparative Example 7, when the content of the phosphinic acid metal salt was further increased in the resin composition, the strands could not be taken out during melt kneading, and the resin composition pellets could not be collected.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de polyamide contenant un polyamide (A), un sel métallique d'acide phosphinique (B), et un composé hydrazine (C) qui présente une structure de phénol encombré. La composition de résine de polyamide est caractérisée en ce que le rapport massique (A/B) de (A) et (B) est de 60/40 à 95/5, et la teneur en (C) est de 0,01 à 5 parties en masse pour 100 parties totales en masse de (A) et (B).
PCT/JP2016/083044 2015-11-12 2016-11-08 Composition de résine de polyamide et article moulé obtenu par moulage de cette dernière WO2017082231A1 (fr)

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WO2018143110A1 (fr) * 2017-02-03 2018-08-09 ユニチカ株式会社 Composition de résine de polyamide et corps moulé formé par moulage de ladite composition
JP2019001996A (ja) * 2017-06-09 2019-01-10 ユニチカ株式会社 ポリアミド樹脂組成物およびそれを成形してなる成形体
CN112437792A (zh) * 2018-07-23 2021-03-02 尤尼吉可株式会社 阻燃性树脂组合物及其制造方法
US11401416B2 (en) 2017-10-17 2022-08-02 Celanese Sales Germany Gmbh Flame retardant polyamide composition

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JP6955763B2 (ja) * 2016-12-15 2021-10-27 ユニチカ株式会社 ポリアミド樹脂組成物およびそれを成形してなる成形体
JP2019026670A (ja) * 2017-07-26 2019-02-21 旭化成株式会社 ポリアミド組成物および成形品
CN109320959B (zh) * 2018-09-25 2021-06-18 深圳市高科塑化有限公司 一种无卤高温尼龙pa6t增强阻燃复合材料及其制备方法
CN110951249B (zh) * 2019-12-20 2022-08-12 广东道生科技股份有限公司 一种高刚性高韧性的mxd6树脂合金工程材料
JPWO2022124100A1 (fr) * 2020-12-07 2022-06-16
CN114085519B (zh) * 2021-11-26 2023-12-19 上海金发科技发展有限公司 一种聚酰胺组合物及其制备方法和应用

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WO2018143110A1 (fr) * 2017-02-03 2018-08-09 ユニチカ株式会社 Composition de résine de polyamide et corps moulé formé par moulage de ladite composition
JP2019001996A (ja) * 2017-06-09 2019-01-10 ユニチカ株式会社 ポリアミド樹脂組成物およびそれを成形してなる成形体
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CN112437792A (zh) * 2018-07-23 2021-03-02 尤尼吉可株式会社 阻燃性树脂组合物及其制造方法

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